Processes for producing saturated alcohols

ABSTRACT

This invention relates in part to processes for producing one or more substituted or unsubstituted saturated alcohols which comprise reacting one or more substituted or unsubstituted alkadienes with carbon monoxide and hydrogen in the presence of a metal-ligand complex catalyst and a promoter and optionally free ligand to produce said one or more substituted or unsubstituted saturated alcohols. The substituted and unsubstituted saturated alcohols produced by the processes of this invention can undergo further reaction(s) to afford desired derivatives thereof. This invention also relates in part to reaction mixtures containing one or more substituted or unsubstituted saturated alcohols as principal product(s) of reaction.

This application is a continuation-in-part of copending U.S. patentapplication Ser. No. 08/843,381, filed Apr. 15, 1997.

BRIEF SUMMARY OF THE INVENTION

Technical Field

This invention relates in part to processes for producing one or moresubstituted or unsubstituted saturated alcohols, e.g., 1-pentanols, orreaction mixtures comprising one or more substituted or unsubstitutedsaturated alcohols. This invention also relates in part to reactionmixtures containing one or more substituted or unsubstituted saturatedalcohols as the principal product(s) of reaction.

BACKGROUND OF THE INVENTION

Saturated alcohols are useful in a variety of applications, e.g.solvents and intermediates. There is a need to produce saturatedalcohols in high selectivities in a manner which can suitably beemployed in a commercial process. Accordingly, it would be desirable toselectively produce saturated alcohols (e.g., 1-pentanols) from arelatively inexpensive starting material (e.g., butadiene) and by aprocess (e.g., hydrocarbonylation) which can be employed commercially.

DISCLOSURE OF THE INVENTION

It has been discovered that alkadienes, e.g., butadiene, can behydrocarbonylated to saturated alcohols, e.g., 1-pentanols, in highselectivities. In particular, it has been surprisingly discovered thatalkadienes can be converted to linear saturated alcohols in highnormal:branched isomer ratios, e.g., butadiene hydrocarbonylated to1-pentanols in high normal:branched isomer ratios. It has beendiscovered that the high selectivities and high normal:branched isomerratios result from conducting the hydrocarbonylation in the presence ofa metal-ligand complex catalyst and optionally free ligand in which theligand is preferably an organophosphine ligand of high basicity and lowsteric bulk and in the presence of a promoter, i.e., an organic orinorganic compound with an ionizable hydrogen of pKa of from about 1 toabout 35.

This invention relates to processes for producing one or moresubstituted or unsubstituted saturated alcohols which comprisesubjecting one or more substituted or unsubstituted alkadienes tohydrocarbonylation in the presence of a hydrocarbonylation catalyst,e.g., metal-organophosphorus ligand complex catalyst, and a promoter andoptionally free ligand to produce said one or more substituted orunsubstituted saturated alcohols. In a preferred embodiment, thehydrocarbonylation catalyst is a metal-organophosphine ligand complexcatalyst and the promoter is the one or more substituted orunsubstituted saturated alcohols and optionally other products of theprocess.

This invention also relates to processes for producing one or moresubstituted or unsubstituted saturated alcohols which comprise reactingone or more substituted or unsubstituted alkadienes with carbon monoxideand hydrogen in the presence of a metal-ligand complex catalyst and apromoter and optionally free ligand to produce said one or moresubstituted or unsubstituted saturated alcohols. In a preferredembodiment, the metal-ligand complex catalyst is ametal-organophosphorus ligand complex catalyst and the promoter is theone or more substituted or unsubstituted saturated alcohols andoptionally other products of the process.

This invention further relates to processes for producing one or moresubstituted or unsubstituted saturated alcohols which comprise reactingone or more substituted or unsubstituted alkadienes with carbon monoxideand hydrogen in the presence of a metal-organophosphorus ligand complexcatalyst and a promoter and optionally free organophosphorus ligand toproduce said one or more substituted or unsubstituted saturatedalcohols. In a preferred embodiment, the metal-organophosphorus ligandcomplex catalyst is a metal-organophosphine ligand complex catalyst andthe promoter is the one or more substituted or unsubstituted saturatedalcohols and optionally other products of the process.

This invention yet further relates to processes for producing one ormore substituted or unsubstituted 1-pentanols which comprise reactingone or more substituted or unsubstituted butadienes with carbon monoxideand hydrogen in the presence of a metal-organophosphorus ligand complexcatalyst and a promoter and optionally free organophosphorus ligand toproduce said one or more substituted or unsubstituted 1-pentanols. In apreferred embodiment, the metal-organophosphorus ligand complex catalystis a metal-organophosphine ligand complex catalyst and the promoter isthe one or more substituted or unsubstituted saturated alcohols andoptionally other products of the process.

This invention also relates in part to a process for producing abatchwise or continuously generated reaction mixture comprising:

(1) one or more substituted or unsubstituted 1-pentanols;

(2) optionally one or more substituted or unsubstituted cis-2-pentenols,trans-2-pentenols, cis-3-pentenols, trans-3-pentenols and/or4-pentenols;

(3) optionally one or more substituted or unsubstituted cis-2-pentenals,trans-2-pentenals, cis-3-pentenals, trans-3-pentenals and/or4-pentenals;

(4) optionally one or more substituted or unsubstituted valeraldehydes;

(5) optionally one or more substituted or unsubstituted lactols, diolsand/or hydroxyaldehydes, e.g., 2-methylvalerolactol,2-ethylbutyrolactol, 2-methyl-1,5-pentanediol, 2-ethyl-1,4-butanediol,1,6-hexanediol and 6-hydroxyhexanal; and

(6) one or more substituted or unsubstituted butadienes, e.g.,butadiene;

wherein the weight ratio of the sum of component (1) to the sum ofcomponents (2), (3), (4) and (5) is greater than about 0.1, preferablygreater than about 0.25, more preferably greater than about 1.0; and theweight ratio of component (6) to the sum of components (1), (2), (3),(4) and (5) is about 0 to about 100, preferably about 0.001 to about 50;which process comprises reacting one or more substituted orunsubstituted butadienes with carbon monoxide and hydrogen in thepresence of a metal-ligand complex catalyst and a promoter andoptionally free ligand to produce said batchwise or continuouslygenerated reaction mixture. In a preferred embodiment, the metal-ligandcomplex catalyst is a metal-organophosphine ligand complex catalyst andthe promoter is the one or more substituted or unsubstituted saturatedalcohols and optionally other products of the process.

This invention further relates to a process for producing a reactionmixture comprising one or more substituted or unsubstituted saturatedalcohols which process comprises reacting one or more substituted orunsubstituted alkadienes with carbon monoxide and hydrogen in thepresence of a metal-ligand complex catalyst and a promoter andoptionally free ligand to produce said reaction mixture comprising oneor more substituted or unsubstituted saturated alcohols. In a preferredembodiment, the metal-ligand complex catalyst is a metal-organophosphineligand complex catalyst and the promoter is the one or more substitutedor unsubstituted saturated alcohols and optionally other products of theprocess.

This invention yet further relates to a process for producing a reactionmixture comprising one or more substituted or unsubstituted 1-pentanolswhich process comprises reacting one or more substituted orunsubstituted butadienes with carbon monoxide and hydrogen in thepresence of a metal-organophosphorus ligand complex catalyst and apromoter and optionally free organophosphorus ligand to produce saidreaction mixture comprising one or more substituted or unsubstituted1-pentanols. In a preferred embodiment, the metal-organophosphorusligand complex catalyst is a metal-organophosphine ligand complexcatalyst and the promoter is the one or more substituted orunsubstituted saturated alcohols and optionally other products of theprocess.

The processes of this invention can achieve high selectivities ofalkadienes to saturated alcohols, e.g., selectivities of butadienes to1-pentanols of up to 75% by weight or greater may be achieved by theprocesses of this invention. The processes of this invention can achievehigh normal:branched isomer ratios of saturated alcohols, e.g.,normal:branched isomer ratios of about 5:1 or greater, preferably about10:1 or greater, and more preferably about 20:1 or greater may beachieved by the processes of this invention.

This invention also relates in part to a batchwise or continuouslygenerated reaction mixture comprising:

(1) one or more substituted or unsubstituted 1-pentanols;

(2) optionally one or more substituted or unsubstituted cis-2-pentenols,trans-2-pentenols, cis-3-pentenols, trans-3-pentenols and/or4-pentenols;

(3) optionally one or more substituted or unsubstituted cis-2-pentenals,trans-2-pentenals, cis-3-pentenals, trans-3-pentenals and/or4-pentenals;

(4) optionally one or more substituted or unsubstituted valeraldehydes;

(5) optionally one or more substituted or unsubstituted lactols, diolsand/or hydroxyaldehydes, e.g., 2-methylvalerolactol,2-ethylbutyrolactol, 2-methyl-1,5-pentanediol, 2-ethyl-1,4-butanediol,1,6-hexanediol and 6-hydroxyhexanal; and

(6) one or more substituted or unsubstituted butadienes, e.g.,butadiene;

wherein the weight ratio of the sum of component (1) to the sum ofcomponents (2), (3), (4) and (5) is greater than about 0.1, preferablygreater than about 0.25, more preferably greater than about 1.0; and theweight ratio of component (6) to the sum of components (1), (2), (3),(4) and (5) is about 0 to about 100, preferably about 0.001 to about 50.

This invention further relates in part to a reaction mixture comprisingone or more substituted or unsubstituted saturated alcohols in whichsaid reaction mixture is prepared by a process which comprises reactingone or more substituted or unsubstituted alkadienes with carbon monoxideand hydrogen in the presence of a metal-ligand complex catalyst and apromoter and optionally free ligand to produce said reaction mixturecomprising one or more substituted or unsubstituted saturated alcohols.In a preferred embodiment, the metal-ligand complex catalyst is ametal-organophosphine ligand complex catalyst and the promoter is theone or more substituted or unsubstituted saturated alcohols andoptionally other products of the process.

This invention yet further relates in part to a reaction mixturecomprising one or more substituted or unsubstituted 1-pentanols in whichsaid reaction mixture is prepared by a process which comprises reactingone or more substituted or unsubstituted butadienes with carbon monoxideand hydrogen in the presence of a metal-organophosphorus ligand complexcatalyst and a promoter and optionally free organophosphorus ligand toproduce said reaction mixture comprising one or more substituted orunsubstituted 1-pentanols. In a preferred embodiment, themetal-organophosphorus ligand complex catalyst is ametal-organophosphine ligand complex catalyst and the promoter is theone or more substituted or unsubstituted saturated alcohols andoptionally other products of the process.

The reaction mixtures of this invention are distinctive insofar as theprocesses for their preparation achieve the generation of highselectivities and high normal:branched isomer ratios of saturatedalcohols, e.g., 1-pentanols, in a manner which can be suitably employedin a commercial process for the manufacture of saturated alcohols. Inparticular, the reaction mixtures of this invention are distinctiveinsofar as the processes for their preparation allow for the productionof 1-pentanols in relatively high yields without generating largeamounts of less desirable byproducts, e.g., one or more substituted orunsubstituted 2-methylbutan-1-ols.

DETAILED DESCRIPTION

The hydrocarbonylation processes of this invention involve convertingone or more substituted or unsubstituted alkadienes to one or moresubstituted or unsubstituted saturated alcohols. The hydrocarbonylationprocesses of this invention may be conducted in one or more steps orstages, preferably a one step process. As used herein, the term"hydrocarbonylation" is contemplated to include all permissiblehydrocarbonylation processes which involve converting one or moresubstituted or unsubstituted alkadienes to one or more substituted orunsubstituted saturated alcohols.

The hydrocarbonylation process involves the production of saturatedalcohols by reacting an alkadiene with carbon monoxide and hydrogen inthe presence of a metal-ligand complex catalyst and optionally freeligand in a liquid medium that also contains a promoter. The reactionmay be carried out in a continuous single pass mode in a continuous gasrecycle manner or more preferably in a continuous liquid catalystrecycle manner as described below. The hydrocarbonylation processingtechniques employable herein may correspond to any known processingtechniques.

The hydrocarbonylation process mixtures employable herein includes anysolution derived from any corresponding hydrocarbonylation process thatmay contain at least some amount of four different main ingredients orcomponents, i.e., the saturated alcohol product, a metal-ligand complexcatalyst, a promoter and optionally free ligand, said ingredientscorresponding to those employed and/or produced by thehydrocarbonylation process from whence the hydrocarbonylation processmixture starting material may be derived. By "free ligand" is meantligand that is not complexed with (tied to or bound to) the metal, e.g.,rhodium atom, of the complex catalyst. It is to be understood that thehydrocarbonylation process mixture compositions employable herein canand normally will contain minor amounts of additional ingredients suchas those which have either been deliberately employed in thehydrocarbonylation process or formed in situ during said process.Examples of such ingredients that can also be present include unreactedalkadiene starting material, carbon monoxide and hydrogen gases, and insitu formed type products, such as saturated alcohols and/or unreactedisomerized olefins corresponding to the alkadiene starting materials,and high boiling liquid byproducts, as well as other inert co-solventtype materials or hydrocarbon additives, if employed.

The catalysts useful in the hydrocarbonylation process includemetal-ligand complex catalysts. The permissible metals which make up themetal-ligand complexes include Group 8, 9 and 10 metals selected fromrhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe),nickel (Ni), palladium (Pd), platinum (Pt), osmium (Os) and mixturesthereof, with the preferred metals being rhodium, cobalt, iridium andruthenium, more preferably rhodium, cobalt and ruthenium, especiallyrhodium. The permissible ligands include, for example, organophosphorus,organoarsenic and organoantimony ligands, or mixtures thereof,preferably organophosphorus ligands. The permissible organophosphorusligands which make up the metal-organophosphorus ligand complexes andfree organophosphorus ligand include mono-, di-, tri- and higherpoly-(organophosphorus) compounds, preferably those of high basicity andlow steric bulk. Illustrative permissible organophosphorus ligandsinclude, for example, organophosphines, organophosphites,organophosphonites, organophosphinites, organophosphorusnitrogen-containing ligands, organophosphorus sulfur-containing ligands,organophosphorus silicon-containing ligands and the like. Otherpermissible ligands include, for example, heteroatom-containing ligandssuch as described in U.S. patent application Ser. No. 08/818,781, filedMar. 10, 1997, the disclosure of which is incorporated herein byreference. Mixtures of such ligands may be employed if desired in themetal-ligand complex catalyst and/or free ligand and such mixtures maybe the same or different. It is to be noted that the successful practiceof this invention does not depend and is not predicated on the exactstructure of the metal-ligand complex species, which may be present intheir mononuclear, dinuclear and/or higher nuclearity forms. Indeed, theexact structure is not known. Although it is not intended herein to bebound to any theory or mechanistic discourse, it appears that thecatalytic species may in its simplest form consist essentially of themetal in complex combination with the ligand and carbon monoxide whenused.

The term "complex" as used herein and in the claims means a coordinationcompound formed by the union of one or more electronically richmolecules or atoms capable of independent existence with one or moreelectronically poor molecules or atoms, each of which is also capable ofindependent existence. For example, the ligands employable herein, i.e.,organophosphorus ligands, may possess one or more phosphorus donoratoms, each having one available or unshared pair of electrons which areeach capable of forming a coordinate covalent bond independently orpossibly in concert (e.g., via chelation) with the metal. Carbonmonoxide (which is also properly classified as a ligand) can also bepresent and complexed with the metal. The ultimate composition of thecomplex catalyst may also contain an additional ligand, e.g., hydrogenor an anion satisfying the coordination sites or nuclear charge of themetal. Illustrative additional ligands include, e.g., halogen (Cl, Br,I), alkyl, aryl, substituted aryl, acyl, CF₃, C₂ F₅, CN, (R)₂ PO andRP(O)(OH)O (wherein each R is the same or different and is a substitutedor unsubstituted hydrocarbon radical, e.g., the alkyl or aryl), acetate,acetylacetonate, SO₄, BF₄, PF₆, NO₂, NO₃, CH₃ O, CH₂ ═CHCH₂, CH₃CH═CHCH₂, C₆ H₅ CN, CH₃ CN, NO, NH₃, pyridine, (C₂ H₅)₃ N, mono-olefins,diolefins and triolefins, tetrahydrofuran, and the like. It is of courseto be understood that the complex species are preferably free of anyadditional organic ligand or anion that might poison the catalyst andhave an undue adverse effect on catalyst performance. It is preferred inthe metal-ligand complex catalyzed hydrocarbonylation processes that theactive catalysts be free of halogen and sulfur directly bonded to themetal, although such may not be absolutely necessary. Preferredmetal-ligand complex catalysts include rhodium-organophosphine ligandcomplex catalysts.

The number of available coordination sites on such metals is well knownin the art. Thus the catalytic species may comprise a complex catalystmixture, in their monomeric, dimeric or higher nuclearity forms, whichare preferably characterized by at least one phosphorus-containingmolecule complexed per metal, e.g., rhodium. As noted above, it isconsidered that the catalytic species of the preferred catalyst employedin the hydrocarbonylation process may be complexed with carbon monoxideand hydrogen in addition to the organophosphorus ligands in view of thecarbon monoxide and hydrogen gas employed by the hydrocarbonylationprocess.

Among the organophosphines that may serve as the ligand of themetal-organophosphine complex catalyst and/or free organophosphineligand of the hydrocarbonylation process mixture starting materials aremono-, di-, tri- and poly-(organophosphines) such astriorganophosphines, trialkylphosphines, alkyldiarylphosphines,dialkylarylphosphines, dicycloalkylarylphosphines,cycloalkyldiarylphosphines, triaralkylphosphines,tricycloalkylphosphines, and triarylphosphines, alkyl and/or aryldiphosphines and bisphosphine mono oxides, as well as ionictriorganophosphines containing at least one ionic moiety selected fromthe salts of sulfonic acid, of carboxylic acid, of phosphonic acid andof quaternary ammonium compounds, and the like. Of course any of thehydrocarbon radicals of such tertiary non-ionic and ionicorganophosphines may be substituted if desired, with any suitablesubstituent that does not unduly adversely affect the desired result ofthe hydrocarbonylation process. The organophosphine ligands employablein the hydrocarbonylation process and/or methods for their preparationare known in the art.

Illustrative triorganophosphine ligands may be represented by theformula: ##STR1## wherein each R¹ is the same or different and is asubstituted or unsubstituted monovalent hydrocarbon radical, e.g., analkyl, cycloalkyl or aryl radical. In a preferred embodiment, each R¹ isthe same or different and is selected from primary alkyl, secondaryalkyl, tertiary alkyl and aryl. Suitable hydrocarbon radicals maycontain from 1 to 24 carbon atoms or greater. Illustrative substituentgroups that may be present on the hydrocarbon radicals include, e.g.,substituted or unsubstituted alkyl radicals, substituted orunsubstituted alkoxy radicals, substituted or unsubstituted silylradicals such as --Si(R²)₃ ; amino radicals such as --N(R²)₂ ; acylradicals such as --C(O)R² ; carboxy radicals such as --C(O)OR² ; acyloxyradicals such as --OC(O)R² ; amido radicals such as --C(O)N(R²)₂ and--N(R²)C(O)R² ; ionic radicals such as --SO₃ M wherein M representsinorganic or organic cationic atoms or radicals; sulfonyl radicals suchas --SO₂ R² ; ether radicals such as --OR² ; sulfinyl radicals such as--SOR² ; selenyl radicals such as --SeR² ; sulfenyl radicals such as--SR² as well as halogen, nitro, cyano, trifluoromethyl and hydroxyradicals, and the like, wherein each R² individually represents the sameor different substituted or unsubstituted monovalent hydrocarbonradical, with the proviso that in amino substituents such as --N(R²)₂,each R² taken together can also represent a divalent bridging group thatforms a heterocyclic radical with the nitrogen atom and in amidosubstituents such as C(O)N(R²)₂ and --N(R²)C(O)R² each --R² bonded to Ncan also be hydrogen. Illustrative alkyl radicals include, e.g., methyl,ethyl, propyl, butyl, octyl, cyclohexyl, isopropyl and the like.Illustrative aryl radicals include, e.g., phenyl, naphthyl,fluorophenyl, difluorophenyl, benzoyloxyphenyl, carboethoxyphenyl,acetylphenyl, ethoxyphenyl, phenoxyphenyl, hydroxyphenyl; carboxyphenyl,trifluoromethylphenyl, methoxyethylphenyl, acetamidophenyl,dimethylcarbamylphenyl, tolyl, xylyl, 4-dimethylaminophenyl,2,4,6-trimethoxyphenyl and the like.

Illustrative specific organophosphines include, e.g.,trimethylphosphine, triethylphosphine, tributylphosphine,trioctylphosphine, diethylbutylphosphine, diethyl-n-propylphosphine,diethylisopropylphosphine, diethylbenzylphosphine,diethylcyclopentylphosphine, diethylcyclohexylphosphine,triphenylphosphine, tris-p-tolylphosphine,tris-p-methoxyphenylphosphine, tris-dimethylaminophenylphosphine,propyldiphenylphosphine, t-butyldiphenylphosphine,n-butyldiphenylphosphine, n-hexyldiphenylphosphine,cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine,tricyclohexylphosphine, tribenzylphosphine, DIOP, i.e.,(4R,5R)-(-)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butaneand/or(4S,5S)-(+)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butaneand/or(4S,5R)-(-)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane,substituted or unsubstituted bicyclic bisphosphines such as1,2-bis(1,4-cyclooctylenephosphino)ethane,1,3-bis(1,4-cyclooctylenephosphino)propane,1,3-bis(1,5-cyclooctylenephosphino)propane and1,2-bis(2,6-dimethyl-1,4-cyclooctylenephosphino)ethane, substituted orunsubstituted bis(2,2'-diphenylphosphinomethyl)biphenyl such asbis(2,2'-diphenylphosphinomethyl)biphenyl andbis{2,2'-di(4-fluorophenyl)phosphinomethyl}biphenyl, MeC(CH₂ PPh₂)₃(triphos), NaO₃ S(C₆ H₄)CH₂ C(CH₂ PPh₂)₃ (sulphos),bis(diphenylphosphino)ferrocene, bis(diisopropylphosphino)ferrocene,bis(diphenylphosphino)ruthenocene, as well as the alkali and alkalineearth metal salts of sulfonated triphenylphosphines, e.g., of(tri-m-sulfophenyl)phosphine and of (m-sulfophenyl)diphenyl-phosphineand the like.

The preferred organophosphorus ligands which make up themetal-organophosphorus ligand complex catalysts and freeorganophosphorus ligands are high basicity ligands. In general, thebasicity of the organophosphorus ligands should be greater than or equalto the basicity of triphenylphosphine (pKb of 2.74), e.g., from about2.74 to about 15. Suitable organophosphorus ligands have a pKb of about3 or greater, preferably a pKb of about 3 to about 12, and morepreferably a pKb of about 5 to about 12. pKb values for illustrativeorganophosphorus ligands useful in this invention are given in the TableI below. In addition, the organophosphorus ligands useful in thisinvention have a steric bulk sufficient to promote thehydrocarbonylation reaction. The steric bulk of monodentateorganophosphorus ligands should be lower than or equal to a Tolman coneangle of 210°, preferably lower than or equal to the steric bulk oftricyclohexylphosphine (Tolman cone angle=170°). Organophosphorusligands having desired basicity and steric bulk include, for example,substituted or unsubstituted tri-primary-alkylphosphines (e.g.,trioctylphosphine, diethylbutylphosphine, diethylisobutylphosphine),di-primary-alkylarylphosphines (e.g., diethylphenylphosphine,diethyl-p-N, N-dimethylphenylphosphine),di-primary-alkyl-mono-secondary-alkylphosphines (e.g.,diethylisopropylphosphine, diethylcyclohexylphosphine),di-primary-alkyl-tert-alkylphosphines (e.g.,diethyl-tert-butylphosphine), mono-primary-alkyl-diarylphosphines (e.g.,diphenylmethylphosphine),mono-primary-alkyl-di-secondary-alkylphosphines (e.g.,dicyclohexylethylphosphine), triarylphosphines (e.g.,tri-para-N,N-dimethylaminophenylphosphine),tri-secondarylalkylphosphines (e.g., tricyclohexylphosphine),mono-primaryalkyl-mono-secondaryalkyl-mono-tertiary alkylphosphines(e.g., ethylisopropyltert-butylphosphine) and the like. The permissibleorganophosphorus ligands may be substituted with any suitablefunctionalities and may include the promoter as described hereinbelow.

                  TABLE I                                                         ______________________________________                                        Organophosphorus Ligand pKb                                                   ______________________________________                                        Trimethylphosphine      8.7                                                     Triethylphosphine 8.7                                                         Tri-n-propylphosphine 8.7                                                     Tri-n-butylphosphine 8.4                                                      Tri-n-octylphosphine 8.4                                                      Tri-tert-butylphosphine 11.4                                                  Diethyl-tert-butylphosphine 10.1                                              Tricyclohexylphosphine 10                                                     Diphenylmethylphosphine 4.5                                                   Diethylphenylphosphine 6.4                                                    Diphenylcyclohexylphosphine 5                                                 Diphenylethylphosphine 4.9                                                    Tri(p-methoxyphenyl)phosphine 4.6                                             Triphenylphosphine 2.74                                                       Tri(p-N,N-dimethylaminophenyl)phosphine 8.65                                  Tri(p-methylphenyl)phosphine 3.84                                           ______________________________________                                    

More particularly, illustrative metal-organophosphine complex catalystsand illustrative free organophosphine ligands include, for example,those disclosed in U.S. Pat. Nos. 3,239,566, 3,527,809; 4,148,830;4,247,486; 4,283,562; 4,400,548; 4,482,749 and 4,861,918, thedisclosures of which are incorporated herein by reference.

Other illustrative permissible organophosphorus ligands which may makeup the metal-organophosphorus ligand complexes and free organophosphorusligands include, for example, those disclosed in U.S. Pat. Nos.4,567,306, 4,599,206, 4,668,651, 4,717,775, 3,415,906, 4,567,306,4,599,206, 4,748,261, 4,769,498, 4,717,775, 4,885,401, 5,202,297,5,235,113, 5,254,741, 5,264,616, 5,312,996, 5,364,950, 5,391,801, U.S.patent application Ser. No. 08/753,505, filed Nov. 26, 1996, and U.S.patent application Ser. No. 08/843,389, filed Apr. 15, 1997, thedisclosures of which are incorporated herein by reference.

The metal-ligand complex catalysts employable in this invention may beformed by methods known in the art. The metal-ligand complex catalystsmay be in homogeneous or heterogeneous form. For instance, preformedmetal hydrido-carbonyl-organophosphorus ligand catalysts may be preparedand introduced into the reaction mixture of a hydrocarbonylationprocess. More preferably, the metal-ligand complex catalysts can bederived from a metal catalyst precursor which may be introduced into thereaction medium for in situ formation of the active catalyst. Forexample, rhodium catalyst precursors such as rhodium dicarbonylacetylacetonate, Rh₂ O₃, Rh₄ (CO)₁₂, Rh₆ (CO)₁₆, Rh(NO₃)₃ and the likemay be introduced into the reaction mixture along with theorganophosphorus ligand for the in situ formation of the activecatalyst. In a preferred embodiment of this invention, rhodiumdicarbonyl acetylacetonate is employed as a rhodium precursor andreacted in the presence of a promoter with the organophosphine ligand toform a catalytic rhodium-organophosphine ligand complex precursor whichis introduced into the reactor along with excess free organophosphineligand for the in situ formation of the active catalyst. In any event,it is sufficient for the purpose of this invention that carbon monoxide,hydrogen and organophosphorus compound are all ligands that are capableof being complexed with the metal and that an activemetal-organophosphorus ligand catalyst is present in the reactionmixture under the conditions used in the hydrocarbonylation process.

More particularly, a catalyst precursor composition can be formedconsisting essentially of a solubilized metal-ligand complex precursorcatalyst, a promoter and free ligand. Such precursor compositions may beprepared by forming a solution of a metal starting material, such as ametal oxide, hydride, carbonyl or salt, e.g. a nitrate, which may or maynot be in complex combination with a ligand as defined herein. Anysuitable metal starting material may be employed, e.g. rhodiumdicarbonyl acetylacetonate, Rh₂ O₃, Rh₄ (CO)₁₂, Rh₆ (CO)₁₆, Rh(NO₃)₃,and organophosphorus ligand rhodium carbonyl hydrides. Carbonyl andorganophosphorus ligands, if not already complexed with the initialmetal, may be complexed to the metal either prior to or in situ duringthe hydrocarbonylation process.

By way of illustration, the preferred catalyst precursor composition ofthis invention consists essentially of a solubilized rhodium carbonylorganophosphine ligand complex precursor catalyst, a promoter and freeorganophosphine ligand prepared by forming a solution of rhodiumdicarbonyl acetylacetonate, a promoter and an organophosphine ligand asdefined herein. The organophosphine ligand readily replaces one of thecarbonyl ligands of the rhodium acetylacetonate complex precursor atroom temperature as witnessed by the evolution of carbon monoxide gas.This substitution reaction may be facilitated by heating the solution ifdesired. Any suitable organic solvent in which both the rhodiumdicarbonyl acetylacetonate complex precursor and rhodium organophosphineligand complex precursor are soluble can be employed. The amounts ofrhodium complex catalyst precursor, organic solvent and organophosphineligand, as well as their preferred embodiments present in such catalystprecursor compositions may obviously correspond to those amountsemployable in the hydrocarbonylation process of this invention.Experience has shown that the acetylacetonate ligand of the precursorcatalyst is replaced after the hydrocarbonylation process has begun witha different ligand, e.g., hydrogen, carbon monoxide or organophosphineligand, to form the active complex catalyst as explained above. In acontinuous process, the acetylacetone which is freed from the precursorcatalyst under hydrocarbonylation conditions is removed from thereaction medium with the product alcohol and thus is in no waydetrimental to the hydrocarbonylation process. The use of such preferredrhodium complex catalytic precursor compositions provides a simpleeconomical and efficient method for handling the rhodium precursor metaland hydrocarbonylation start-up.

Accordingly, the metal-ligand complex catalysts used in the process ofthis invention consists essentially of the metal complexed with carbonmonoxide and a ligand, said ligand being bonded (complexed) to the metalin a chelated and/or non-chelated fashion. Moreover, the terminology"consists essentially of", as used herein, does not exclude, but ratherincludes, hydrogen complexed with the metal, in addition to carbonmonoxide and the ligand. Further, such terminology does not exclude thepossibility of other organic ligands and/or anions that might also becomplexed with the metal. Materials in amounts which unduly adverselypoison or unduly deactivate the catalyst are not desirable and so thecatalyst most desirably is free of contaminants such as metal-boundhalogen (e.g., chlorine, and the like) although such may not beabsolutely necessary. The hydrogen and/or carbonyl ligands of an activemetal-organophosphine ligand complex catalyst may be present as a resultof being ligands bound to a precursor catalyst and/or as a result of insitu formation, e.g., due to the hydrogen and carbon monoxide gasesemployed in hydrocarbonylation process of this invention.

As noted the hydrocarbonylation process involves the use of ametal-ligand complex catalyst as described herein. Of course mixtures ofsuch catalysts can also be employed if desired. The amount ofmetal-ligand complex catalyst present in the reaction medium of a givenhydrocarbonylation process need only be that minimum amount necessary toprovide the given metal concentration desired to be employed and whichwill furnish the basis for at least the catalytic amount of metalnecessary to catalyze the particular hydrocarbonylation process involvedsuch as disclosed, for example, in the above-mentioned patents. Ingeneral, the catalyst concentration can range from several parts permillion to several percent by weight. Organophosphorus ligands can beemployed in the above-mentioned catalysts in a molar ratio of generallyfrom about 0.5:1 or less to about 1000:1 or greater. The catalystconcentration will be dependent on the hydrocarbonylation processconditions and solvent employed.

In general, the organophosphorus ligand concentration inhydrocarbonylation process mixtures may range from between about 0.005and 25 weight percent based on the total weight of the reaction mixture.Preferably the ligand concentration is between 0.01 and 15 weightpercent, and more preferably is between about 0.05 and 10 weight percenton that basis.

In general, the concentration of the metal in the hydrocarbonylationprocess mixtures may be as high as about 2000 parts per million byweight or greater based on the weight of the reaction mixture.Preferably the metal concentration is between about 50 and 1500 partsper million by weight based on the weight of the reaction mixture, andmore preferably is between about 70 and 1200 parts per million by weightbased on the weight of the reaction mixture.

In addition to the metal-ligand complex catalyst, free ligand (i.e.,ligand that is not complexed with the rhodium metal) may also be presentin the hydrocarbonylation process medium. The free ligand may correspondto any of the above-defined ligands discussed above as employableherein. It is preferred that the free ligand be the same as the ligandof the metal-ligand complex catalyst employed. However, such ligandsneed not be the same in any given process. The hydrocarbonylationprocess may involve up to 100 moles, or higher, of free ligand per moleof metal in the hydrocarbonylation process medium. Preferably thehydrocarbonylation process is carried out in the presence of from about1 to about 50 moles of coordinatable phosphorus, more preferably fromabout 1 to about 20 moles of coordinatable phosphorus, and mostpreferably from about 1 to about 8 moles of coordinatable phosphorus,per mole of metal present in the reaction medium; said amounts ofcoordinatable phosphorus being the sum of both the amount ofcoordinatable phosphorus that is bound (complexed) to the rhodium metalpresent and the amount of free (non-complexed) coordinatable phosphoruspresent. Of course, if desired, make-up or additional coordinatablephosphorus can be supplied to the reaction medium of thehydrocarbonylation process at any time and in any suitable manner, e.g.to maintain a predetermined level of free ligand in the reaction medium.

As indicated above, the hydrocarbonylation catalyst may be inheterogeneous form during the reaction and/or during the productseparation. Such catalysts are particularly advantageous in thehydrocarbonylation of alkadienes to produce high boiling or thermallysensitive alcohols, so that the catalyst may be separated from theproducts by filtration or decantation at low temperatures. For example,the rhodium catalyst may be attached to a support so that the catalystretains its solid form during both the hydrocarbonylation and separationstages, or is soluble in a liquid reaction medium at high temperaturesand then is precipitated on cooling.

As an illustration, the rhodium catalyst may be impregnated onto anysolid support, such as inorganic oxides, (e.g., alumina, silica,titania, or zirconia) carbon, or ion exchange resins. The catalyst maybe supported on, or intercalated inside the pores of, a zeolite orglass; the catalyst may also be dissolved in a liquid film coating thepores of said zeolite or glass. Such zeolite-supported catalysts areparticularly advantageous for producing one or more regioisomericalcohols in high selectivity, as determined by the pore size of thezeolite. The techniques for supporting catalysts on solids, such asincipient wetness, which will be known to those skilled in the art. Thesolid catalyst thus formed may still be complexed with one or more ofthe ligands defined above. Descriptions of such solid catalysts may befound in for example: J. Mol. Cat. 1991, 70, 363-368; Catal. Lett. 1991,8, 209-214; J. Organomet. Chem, 1991, 403, 221-227; Nature, 1989, 339,454-455; J. Catal. 1985, 96, 563-573; J. Mol. Cat. 1987, 39, 243-259.

The rhodium catalyst may be attached to a thin film or membrane support,such as cellulose acetate or polyphenylenesulfone, as described in forexample J. Mol. Cat. 1990, 63, 213-221.

The rhodium catalyst may be attached to an insoluble polymeric supportthrough an organophosphorus-containing ligand, such as a phosphine orphosphite, incorporated into the polymer. Such polymer-supported ligandsare well known, and include such commercially available species as thedivinylbenzene/polystyrene-supported triphenylphosphine. The supportedligand is not limited by the choice of polymer or phosphorus-containingspecies incorporated into it. Descriptions of polymer-supportedcatalysts may be found in for example: J. Mol. Cat. 1993, 83, 17-35;Chemtech 1983, 46; J. Am. Chem. Soc. 1987, 109, 7122-7127.

In the heterogeneous catalysts described above, the catalyst may remainin its heterogeneous form during the entire hydrocarbonylation andcatalyst separation process. In another embodiment of the invention, thecatalyst may be supported on a polymer which, by the nature of itsmolecular weight, is soluble in the reaction medium at elevatedtemperatures, but precipitates upon cooling, thus facilitating catalystseparation from the reaction mixture. Such "soluble" polymer-supportedcatalysts are described in for example: Polymer, 1992, 33, 161; J. Org.Chem. 1989, 54, 2726-2730.

When the rhodium catalyst is in a heterogeneous or supported form, thereaction may be carried out in the gas phase. More preferably, thereaction is carried out in the slurry phase due to the high boilingpoints of the products, and to avoid decomposition of the productalcohols. The catalyst may then be separated from the product mixture byfiltration or decantation.

The processes of this invention can be operated over a wide range ofreaction rates (m/L/h=moles of product/liter of reaction solution/hour).Typically, the reaction rates are at least 0.01 m/L/h or higher,preferably at least 0.1 m/L/h or higher, and more preferably at least0.3 m/L/h or higher. Higher reaction rates are generally preferred froman economic standpoint, e.g., smaller reactor size, etc.

The substituted and unsubstituted alkadiene starting materials useful inthe hydrocarbonylation processes include, but are not limited to,conjugated aliphatic diolefins represented by the formula: ##STR2##wherein R₁ and R₂ are the same or different and are hydrogen, halogen ora substituted or unsubstituted hydrocarbon radical. The alkadienes canbe linear or branched and can contain substituents (e.g., alkyl groups,halogen atoms, amino groups or silyl groups). Illustrative of suitablealkadiene starting materials are butadiene, isoprene, dimethylbutadiene, cyclopentadiene and chloroprene. Most preferably, thealkadiene starting material is butadiene itself (CH₂ ═CH--CH═CH₂). Forpurposes of this invention, the term "alkadiene" is contemplated toinclude all permissible substituted and unsubstituted conjugateddiolefins, including all permissible mixtures comprising one or moresubstituted and unsubstituted conjugated diolefins. Illustrative ofsuitable substituted and unsubstituted alkadienes (including derivativesof alkadienes) include those permissible substituted and unsubstitutedalkadienes described in Kirk-Othmer, Encyclopedia of ChemicalTechnology, Fourth Edition, 1996, the pertinent portions of which areincorporated herein by reference.

The particular hydrocarbonylation reaction conditions are not narrowlycritical and can be any effective hydrocarbonylation proceduressufficient to produce one or more saturated alcohols. The exact reactionconditions will be governed by the best compromise between achievinghigh catalyst selectivity, activity, lifetime and ease of operability,as well as the intrinsic reactivity of the starting materials inquestion and the stability of the starting materials and the desiredreaction product to the reaction conditions. The hydrocarbonylationprocess conditions may include any suitable type hydrocarbonylationconditions heretofore employed for producing alcohols. The totalpressure employed in the hydrocarbonylation process may range in generalfrom about 1 to about 10,000 psia, preferably from about 20 to 3000 psiaand more preferably from about 50 to about 2000 psia. The total pressureof the hydrocarbonylation process will be dependent on the particularcatalyst system employed.

More specifically, the carbon monoxide partial pressure of thehydrocarbonylation process in general may range from about 1 to about3000 psia, and preferably from about 3 to about 1500 psia, while thehydrogen partial pressure in general may range from about 1 to about3000 psia, and preferably from about 3 to about 1500 psia. In general,the molar ratio of carbon monoxide to gaseous hydrogen may range fromabout 100:1 or greater to about 1:100 or less, the preferred carbonmonoxide to gaseous hydrogen molar ratio being from about 1:10 to about10:1. The carbon monoxide and hydrogen partial pressures will bedependent in part on the particular catalyst system employed. It isunderstood that carbon monoxide and hydrogen can be employed separately,either alone or in mixture with each other, i.e., synthesis gas, or maybe produced in situ under reaction conditions and/or be derived from thepromoter or solvent (not necessarily involving free hydrogen or carbonmonoxide). In an embodiment, the hydrogen partial pressure and carbonmonoxide partial pressure are sufficient to prevent or minimizederivatization, e.g., further hydrocarbonylation of penten-1-ols.

In conducting the process of this invention, it may be desirable tomaintain some alkadiene partial pressure or when the alkadieneconversion is complete, the carbon monoxide and hydrogen partialpressures should be sufficient to prevent or minimize derivatization,e.g., further hydrocarbonylation of penten-1-ols. The alkadiene partialpressure of the hydrocarbonylation process may vary over a wide range.For example, the alkadiene, e.g., butadiene, hydrocarbonylation may beconducted at an alkadiene partial pressure of greater than 0 psi, ifdesired greater than 5 psi.

Further, the hydrocarbonylation process may be conducted at a reactiontemperature from about 20° C. to about 200° C., preferably from about50° C. to about 150° C., and more preferably from about 65° C. to about115° C. The temperature must be sufficient for reaction to occur (whichmay vary with catalyst system employed), but not so high that ligand orcatalyst decomposition occurs.

The hydrocarbonylation process may be conducted at a residence time offrom about 10 minutes or less to about 10 hours or longer, preferablyfrom about 30 minutes to about 8 hours, and more preferably from about90 minutes to about 4 hours. The residence time must be sufficient forreaction to occur (which may vary with catalyst system employed), butnot so long that ligand or catalyst decomposition occurs.

Of course, it is to be also understood that the hydrocarbonylationprocess conditions employed will be governed by the type of saturatedalcohol product desired.

The hydrocarbonylation process is also conducted in the presence of apromoter. As used herein, "promoter" means an organic or inorganiccompound with an ionizable hydrogen of pKa of from about 1 to about 35.Illustrative promoters include, for example, protic solvents, organicand inorganic acids, alcohols, water, phenols, thiols, thiophenols,nitroalkanes, ketones, nitriles, amines (e.g., pyrroles anddiphenylamine), amides (e.g., acetamide), mono-, di- andtrialkylammonium salts, and the like. Approximate pKa values forillustrative promoters useful in this invention are given in the TableII below. The promoter may be present in the hydrocarbonylation reactionmixture either alone or incorporated into the ligand structure, eitheras the metal-ligand complex catalyst or as free ligand, or into thealkadiene structure. The desired promoter will depend on the nature ofthe ligands and metal of the metal-ligand complex catalysts. In general,a catalyst with a more basic metal-bound acyl or other intermediate willrequire a lower concentration and/or a less acidic promoter.

Although it is not intended herein to be bound to any theory ormechanistic discourse, it appears that the promoter may function totransfer a hydrogen ion to or otherwise activate a catalyst-bound acylor other intermediate. Mixtures of promoters in any permissiblecombination may be useful in this invention. A preferred class ofpromoters includes those that undergo hydrogen bonding, e.g., NH, OH andSH-containing groups and Lewis acids, since this is believed tofacilitate hydrogen ion transfer to or activation of the metal-boundacyl or other intermediate. In general, the amount of promoter may rangefrom about 10 parts per million or so up to about 99 percent by weightor more based on the total weight of the hydrocarbonylation processmixture starting materials.

                  TABLE II                                                        ______________________________________                                        Promoter             pKa                                                      ______________________________________                                        ROH (R = alkyl)      15-19                                                      ROH (R = aryl)  8-11                                                          RCONHR (R = hydrogen or alkyl, 15-19                                          e.g., acetamide)                                                              R.sub.3 NH.sup.+, R.sub.2 NH.sub.2.sup.+  (R = alkyl) 10-11                   RCH.sub.2 NO.sub.2  8-11                                                      RCOCH.sub.2 R (R = alkyl) 19-20                                               RSH (R = alkyl) 10-11                                                         RSH (R = aryl)  8-11                                                          CNCH.sub.2 CN 11                                                              Diarylamine 21-24                                                             Pyrrole 20                                                                    Pyrrolidine 34                                                              ______________________________________                                    

The concentration of the promoter employed will depend upon the detailsof the catalyst system employed. Without wishing to be bound by theory,the promoter component must be sufficiently acidic and in sufficientconcentration to transfer a hydrogen ion to or otherwise activate thecatalyst-bound acyl or other intermediate. It is believed that apromoter component acidity or concentration which is insufficient totransfer a hydrogen ion to or otherwise activate the catalyst-bound acylor other intermediate will result in the formation of pentenal products,rather than the preferred 1-pentanol products. The ability of a promotercomponent to transfer a hydrogen ion to or otherwise activate thecatalyst-bound acyl or other intermediate may be governed by severalfactors, for example, the concentration of the promoter component, theintrinsic acidity of the promoter component (the pKa), the compositionof the reaction medium (e.g., the reaction solvent) and the temperature.Promoters are chosen on the basis of their ability to transfer ahydrogen ion to or otherwise activate such a catalyst-bound acyl orother intermediate under reaction conditions sufficient to result in theformation of alcohol products, but not so high as to result indetrimental side reactions of the catalyst, reactants or products. Incases where the promoter component acidity or concentration isinsufficient to do so, aldehyde products (e.g., pentenals) are initiallyformed which may or may not be subsequently converted to saturatedalcohols, e.g., 1-pentanols.

In general, a less basic metal-bound acyl will require a higherconcentration of the promoter component or a more acidic promotercomponent to protonate or otherwise activate it fully, such that theproducts are more desired 1-pentanols, rather than pentenals. This canbe achieved by appropriate choice of promoter component. For example, anenabling concentration of protonated or otherwise activatedcatalyst-bound acyl or other intermediate can be achieved though the useof a large concentration of a mildly acidic promoter component, orthrough the use of a smaller concentration of a more acidic component.The promoter component is selected based upon its ability to produce thedesired concentration of protonated or otherwise activatedcatalyst-bound acyl or other intermediate in the reaction medium underreaction conditions. In general, the intrinsic strength of an acidicmaterial is generally defined in aqueous solution as the pKa, and not inreaction media commonly employed in hydrocarbonylation. The choice ofthe promoter and its concentration is made based in part upon thetheoretical or equivalent pH that the promoter alone at suchconcentration gives in aqueous solution at 22° C. The desiredtheoretical or equivalent pH of promoter component solutions should begreater than 0, preferably from about 1-12, more preferably from about2-10 and most preferably from 4-8. The theoretical or equivalent pH canbe readily calculated from values of pKa's at the appropriate promotercomponent concentration by reference to standard tables such as thosefound in "Ionization Constants of Organic Acids in Aqueous Solution"(IUPAC Chemical Data Series--No. 23) by E. P Serjeant and Boyd Dempsey,Pergamon Press (1979) and "Dissociation Constants of Inorganic Acids andBases in Aqueous Solution" (IUPAC Chemical Data Series--No. 19, by D. D.Perrin, Pergamon Press.

Depending on the particular catalyst and reactants employed, suitablepromoters preferably include solvents, for example, alcohols (e.g., thesaturated alcohol products such as 1-pentanols), thiols, thiophenols,selenols, tellurols, alkenes, alkynes, aldehydes, higher boilingbyproducts, ketones, esters, amides, primary and secondary amines,alkylaromatics and the like. Any suitable promoter which does not undulyadversely interfere with the intended hydrocarbonylation process can beemployed. Permissible protic solvents have a pKa of about 1-35,preferably a pKa of about 3-30, and more preferably a pKa of about 5-25.Mixtures of one or more different solvents may be employed if desired.

In general, with regard to the production of saturated alcohols, it ispreferred to employ saturated alcohol promoters corresponding to thesaturated alcohol products desired to be produced and/or higher boilingbyproducts as the main protic solvents. Such byproducts can also bepreformed if desired and used accordingly. Illustrative preferred proticsolvents employable in the production of saturated alcohols, e.g.,1-pentanols, include alcohols (e.g., pentenols, octanols, hexanediols),amines, thiols, thiophenols, ketones (e.g. acetone and methylethylketone), hydroxyaldehydes (e.g., 6-hydroxyaldehyde), lactols (e.g.,2-methylvalerolactol), esters (e.g. ethyl acetate), hydrocarbons (e.g.diphenylmethane, triphenylmethane), nitrohydrocarbons (e.g.nitromethane), 1,4-butanediols and sulfolane. Suitable protic solventsare disclosed in U.S. Pat. No. 5,312,996.

As indicated above, the promoter may be incorporated into the ligandstructure, either as the metal-ligand complex catalyst or as freeligand. Suitable organophosphorus ligand promoters which may be usefulin this invention include, for example, tris(2-hydroxyethyl)phosphine,tris(3-hydroxypropyl)phosphine, tris(2-hydroxyphenylphosphine),tris(4-hydroxyphenylphosphine), tris(3-carboxypropyl)phosphine,tris(3-carboxamidopropyl)phosphine, diphenyl(2-hydroxyphenyl)phosphine,diethyl(2-anilinophenyl)phosphine, and tris(3-pyrroyl)phosphine. The useof ligand promoters may by particularly beneficial in those instanceswhen the saturated alcohol product is not effective as a promoter. Aswith the organophosphorus ligands which make up themetal-organophosphorus ligand complex catalysts and freeorganophosphorus ligands, the organophosphorus ligand promoterspreferably are high basicity ligands having a steric bulk lower than orequal to a Tolman cone angle of 210°, preferably lower than or equal tothe steric bulk of tricyclohexylphosphine (Tolman cone angle=170°).Indeed, the organophosphorus ligand promoters may be employed asorganophosphorus ligands which make up the metal-organophosphorus ligandcomplex catalysts and free organophosphorus ligands. Mixtures ofpromoters comprising one or more organophosphorus ligand promoters andmixtures comprising one or more organophosphorus ligand promoters andone or more other promoters, e.g., protic solvents, may be useful inthis invention.

In an embodiment of the invention, the hydrocarbonylation processmixture may consist of one or more liquid phases, e.g. a polar and anonpolar phase. Such processes are often advantageous in, for example,separating products from catalyst and/or reactants by partitioning intoeither phase. In addition, product selectivities dependent upon solventproperties may be increased by carrying out the reaction in thatsolvent. An application of this technology is the aqueous-phasehydrocarbonylation of alkadienes employing sulfonated phosphine ligands,hydroxylated phosphine ligands and aminated phosphine ligands for therhodium catalyst. A process carried out in aqueous solvent isparticularly advantageous for the preparation of alcohols because theproducts may be separated from the catalyst by extraction into asolvent.

As described herein, the phosphorus-containing ligand for the rhodiumhydrocarbonylation catalyst may contain any of a number of substituents,such as cationic or anionic substituents, which will render the catalystsoluble in a polar phase, e.g. water. Optionally, a phase-transfercatalyst may be added to the reaction mixture to facilitate transport ofthe catalyst, reactants, or products into the desired solvent phase. Thestructure of the ligand or the phase-transfer catalyst is not criticaland will depend on the choice of conditions, reaction solvent, anddesired products.

When the catalyst is present in a multiphasic system, the catalyst maybe separated from the reactants and/or products by conventional methodssuch as extraction or decantation. The reaction mixture itself mayconsist of one or more phases; alternatively, the multiphasic system maybe created at the end of the reaction by for example addition of asecond solvent to separate the products from the catalyst. See, forexample, U.S. Pat. No. 5,180,854, the disclosure of which isincorporated herein by reference.

In an embodiment of the process of this invention, an olefin can behydrocarbonylated along with an alkadiene using the above-describedmetal-ligand complex catalysts. In such cases, an alcohol derivative ofthe olefin is also produced along with the saturated alcohols, e.g.,1-pentanols.

Mixtures of different olefinic starting materials can be employed, ifdesired, in the hydrocarbonylation processes. More preferably thehydrocarbonylation process is especially useful for the production ofsaturated alcohols, by hydroformylating alkadienes in the presence ofalpha olefins containing from 2 to 30, preferably 4 to 20, carbon atoms,including isobutylene, and internal olefins containing from 4 to 20carbon atoms as well as starting material mixtures of such alpha olefinsand internal olefins. Commercial alpha olefins containing four or morecarbon atoms may contain minor amounts of corresponding internal olefinsand/or their corresponding saturated hydrocarbon and that suchcommercial olefins need not necessarily be purified from same prior tobeing hydroformylated.

Illustrative of other olefinic starting materials include alpha-olefins,internal olefins, 1,3-dienes, 1,2-dienes, alkyl alkenoates, alkenylalkanoates, alkenyl alkyl ethers, alkenols, alkenals, and the like,e.g., ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene,1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene,1-eicosene, 2-butene, 2-methyl propene (isobutylene), 2-methylbutene,2-pentene, 2-hexene, 3-hexane, 2-heptene, cyclohexene, propylene dimers,propylene trimers, propylene tetramers, piperylene, isoprene,2-ethyl-1-hexene, 2-octene, styrene, 3-phenyl-1-propene, 1,4-hexadiene,1,7-octadiene, 3-cyclohexyl-1-butene, allyl alcohol, allyl butyrate,hex-1-en-4-ol, oct-1-en-4-ol, vinyl acetate, allyl acetate, 3-butenylacetate, vinyl propionate, allyl propionate, methyl methacrylate, vinylethyl ether, vinyl methyl ether, vinyl cyclohexene, allyl ethyl ether,methyl pentenoate, n-propyl-7-octenoate, pentenals, e.g., 2-pentenal,3-pentenal and 4-pentenal; 1-pentanols, e.g., 2-1-pentanol, 3-1-pentanoland 4-1-pentanol; 3-butenenitrile, 3-pentenenitrile, 5-hexenamide,4-methyl styrene, 4-isopropyl styrene, 4-tert-butyl styrene,alpha-methyl styrene, 4-tert-butyl-alpha-methyl styrene,1,3-diisopropenylbenzene, eugenol, iso-eugenol, safrole, iso-safrole,anethol, 4-allylanisole, indene, limonene, beta-pinene,dicyclopentadiene, cyclooctadiene, camphene, linalool, and the like.Other illustrative olefinic compounds may include, for example,p-isobutylstyrene, 2-vinyl-6-methoxynaphthylene, 3-ethenylphenyl phenylketone, 4-ethenylphenyl-2-thienylketone, 4-ethenyl-2-fluorobiphenyl,4-(1,3-dihydro-1-oxo-2H-isoindol-2-yl)styrene,2-ethenyl-5-benzoylthiophene, 3-ethenylphenyl phenyl ether,propenylbenzene, isobutyl-4-propenylbenzene, phenyl vinyl ether and thelike. Other olefinic compounds include substituted aryl ethylenes asdescribed in U.S. Pat. No. 4,329,507, the disclosure of which isincorporated herein by reference.

In those instances where the promoter is not the solvent, thehydrocarbonylation processes encompassed by this invention are conductedin the presence of an organic solvent for the metal ligand complexcatalyst and free ligand. The solvent may also contain dissolved waterup to the saturation limit. Depending on the particular catalyst andreactants employed, suitable organic solvents include, for example,alcohols, alkanes, alkenes, alkynes, ethers, aldehydes, higher boilinghydrocarbonylation byproducts, ketones, esters, amides, tertiary amines,aromatics and the like. Any suitable solvent which does not undulyadversely interfere with the intended hydrocarbonylation reaction can beemployed. Mixtures of one or more different solvents may be employed ifdesired. Illustrative preferred solvents employable in the production ofalcohols include ketones (e.g. acetone and methylethyl ketone), esters(e.g. ethyl acetate), hydrocarbons (e.g. toluene), nitrohydrocarbons(e.g. nitrobenzene), ethers (e.g. tetrahydrofuran (THF) and sulfolane.Suitable solvents are disclosed in U.S. Pat. No. 5,312,996. The amountof solvent employed is not critical to the subject invention and needonly be that amount sufficient to solubilize the catalyst and freeligand of the hydrocarbonylation reaction mixture to be treated. Ingeneral, the amount of solvent may range from about 5 percent by weightup to about 99 percent by weight or more based on the total weight ofthe hydrocarbonylation reaction mixture starting material.

Illustrative substituted and unsubstituted saturated alcohols that canbe prepared by the processes of this invention include one or more ofthe following: alkanols such as 1-pentanols, 1-hexanols, includingmixtures comprising one or more of the above saturated alcohols.Illustrative of suitable substituted and unsubstituted saturatedalcohols (including derivatives of saturated alcohols) include thosepermissible substituted and unsubstituted saturated alcohols which aredescribed in Kirk-Othmer, Encyclopedia of Chemical Technology, FourthEdition, 1996, the pertinent portions of which are incorporated hereinby reference.

As indicated above, it is generally preferred to carry out thehydrocarbonylation process of this invention in a continuous manner. Ingeneral, continuous hydrocarbonylation processes may involve: (a)hydrocarbonylating the alkadiene starting material(s) with carbonmonoxide and hydrogen in a liquid homogeneous reaction mixturecomprising a solvent, the metal-ligand complex catalyst, and freeligand; (b) maintaining reaction temperature and pressure conditionsfavorable to the hydrocarbonylation of the alkadiene startingmaterial(s); (c) supplying make-up quantities of the alkadiene startingmaterial(s), carbon monoxide and hydrogen to the reaction medium asthose reactants are used up; and (d) recovering the desired alcoholhydrocarbonylation product(s) in any manner desired. The continuousreaction can be carried out in a single pass mode, i.e., wherein avaporous mixture comprising unreacted alkadiene starting material(s) andvaporized alcohol product is removed from the liquid reaction mixturefrom whence the alcohol product is recovered and make-up alkadienestarting material(s), carbon monoxide and hydrogen are supplied to theliquid reaction medium for the next single pass through withoutrecycling the unreacted alkadiene starting material(s). However, it isgenerally desirable to employ a continuous reaction that involves eithera liquid and/or gas recycle procedure. Such types of recycle procedureare known in the art and may involve the liquid recycling of themetal-ligand complex catalyst solution separated from the desiredalcohol reaction product(s).

As indicated above, the hydrocarbonylation process may involve a liquidcatalyst recycle procedure. Such liquid catalyst recycle procedures areknown in the art. For instance, in such liquid catalyst recycleprocedures it is commonplace to continuously or intermittently remove aportion of the liquid reaction product medium, containing, e.g., thealcohol product, the solubilized metal-ligand complex catalyst, freeligand, and organic solvent, as well as byproducts produced in situ bythe hydrocarbonylation and unreacted alkadiene starting material, carbonmonoxide and hydrogen (syn gas) dissolved in said medium, from thehydrocarbonylation reactor, to a distillation zone, e.g., avaporizer/separator wherein the desired alcohol product is distilled inone or more stages under normal, reduced or elevated pressure, asappropriate, and separated from the liquid medium. The vaporized ordistilled desired alcohol product so separated may then be condensed andrecovered in any conventional manner as discussed above. The remainingnon-volatilized liquid residue which contains metal-ligand complexcatalyst, solvent, free ligand and usually some undistilled alcoholproduct is then recycled back, with or with out further treatment asdesired, along with whatever by-product and non-volatilized gaseousreactants that might still also be dissolved in said recycled liquidresidue, in any conventional manner desired, to the hydrocarbonylationreactor, such as disclosed e.g., in the above-mentioned patents.Moreover the reactant gases so removed by such distillation from thevaporizer may also be recycled back to the reactor if desired.

Recovery and purification of saturated alcohols may be by anyappropriate means, and may include distillation, phase separation,extraction, precipitation, absorption, crystallization, membraneseparation, derivative formation and other suitable means. For example,a crude reaction product can be subjected to a distillation-separationat atmospheric or reduced pressure through a packed distillation column.Reactive distillation may be useful in conducting the hydrocarbonylationreaction.

As indicated above, at the conclusion of (or during) thehydrocarbonylation process, the desired saturated alcohols, e.g.,1-pentanols, may be recovered from the reaction mixtures used in theprocess of this invention. For instance, in a continuous liquid catalystrecycle reaction the portion of the liquid reaction mixture (containing1-pentanol product, catalyst, etc.) removed from the reactor can bepassed to a vaporizer/separator wherein the desired alcohol product canbe separated via distillation, in one or more stages, under normal,reduced or elevated pressure, from the liquid reaction solution,condensed and collected in a product receiver, and further purified ifdesired. The remaining non-volatilized catalyst containing liquidreaction mixture may then be recycled back to the reactor as may, ifdesired, any other volatile materials, e.g., unreacted alkadiene,together with any hydrogen and carbon monoxide dissolved in the liquidreaction after separation thereof from the condensed 1-pentanol product,e.g., by distillation in any conventional manner. It is generallydesirable to employ an organophosphorus ligand whose molecular weightexceeds that of the higher boiling alcohol oligomer byproductcorresponding to the 1-pentanols being produced in thehydrocarbonylation process. Another suitable recovery technique issolvent extraction or crystallization. In general, it is preferred toseparate the desired saturated alcohols from the catalyst-containingreaction mixture under reduced pressure and at low temperatures so as toavoid possible degradation of the organophosphorus ligand and reactionproducts. When an alpha-mono-olefin reactant is also employed, thealcohol derivative thereof can also be separated by the above methods.

More particularly, distillation and separation of the desired alcoholproduct from the metal-ligand complex catalyst containing productsolution may take place at any suitable temperature desired. In general,it is recommended that such distillation take place at relatively lowtemperatures, such as below 150° C., and more preferably at atemperature in the range of from about 50° C. to about 130° C. It isalso generally recommended that such alcohol distillation take placeunder reduced pressure, e.g., a total gas pressure that is substantiallylower than the total gas pressure employed during hydrocarbonylationwhen low boiling alcohols (e.g., C₅ and C₆) are involved or under vacuumwhen high boiling alcohols (e.g. C₇ or greater) are involved. Forinstance, a common practice is to subject the liquid reaction productmedium removed from the hydrocarbonylation reactor to a pressurereduction so as to volatilize a substantial portion of the unreactedgases dissolved in the liquid medium which now contains a much lowersynthesis gas concentration than was present in the hydrocarbonylationprocess medium to the distillation zone, e.g. vaporizer/separator,wherein the desired alcohol product is distilled. In general,distillation pressures ranging from vacuum pressures on up to total gaspressure of about 50 psig should be sufficient for most purposes.

While not wishing to be bound to any particular reaction mechanism, itis believed that the overall hydrocarbonylation reaction generallyproceeds in one step, i.e., the one or more substituted or unsubstitutedalkadienes (e.g., butadiene) are converted to one or more substituted orunsubstituted saturated alcohols (e.g., 1-pentanol) either directly orthrough one or more intermediates (e.g., a 3-pentenal/ol and/or4-pentenal/ol). This invention is not intended to be limited in anymanner by any particular reaction mechanism, but rather encompasses allpermissible reaction mechanisms involved in hydrocarbonylating one ormore substituted or unsubstituted alkadienes with carbon monoxide andhydrogen in the presence of a metal-ligand complex catalyst and apromoter and optionally free ligand to produce one or more substitutedor unsubstituted saturated alcohols.

The saturated alcohol products have a wide range of utilities that arewell known in the art, e.g., they are useful as startingmaterials/intermediates in chemical syntheses.

A process involving the hydrocarbonylation of one or more substituted orunsubstituted alkadienes to produce one or more substituted orunsubstituted unsaturated alcohols is disclosed in copending U.S. patentapplication Ser. No. 08/843,381, filed Apr. 15, 1997, the disclosure ofwhich is incorporated herein by reference. A process involving thereductive hydroformylation of one or more substituted or unsubstitutedalkadienes to produce one or more substituted or unsubstituted alkenolsis disclosed in copending U.S. patent application Ser. No. 08/842,666,filed Apr. 15, 1997, the disclosure of which is incorporated herein byreference. Another process involving the production of one or moresubstituted or unsubstituted alkenals and/or alkenols byhydroformylation and/or hydroformylation/hydrogenation is disclosed incopending U.S. patent application Ser. No. 08/843,389, filed Apr. 15,1997, the disclosure of which is incorporated herein by reference.

The hydrocarbonylation processes of this invention may be carried outusing, for example, a fixed bed reactor, a fluid bed reactor, acontinuous stirred tank reactor (CSTR) or a slurry reactor. The optimumsize and shape of the catalysts will depend on the type of reactor used.In general, for fluid bed reactors, a small, spherical catalyst particleis preferred for easy fluidization. With fixed bed reactors, largercatalyst particles are preferred so the back pressure within the reactoris kept reasonably low.

The hydrocarbonylation processes of this invention can be conducted in abatch or continuous fashion, with recycle of unconsumed startingmaterials if required. The reaction can be conducted in a singlereaction zone or in a plurality of reaction zones, in series or inparallel or it may be conducted batchwise or continuously in anelongated tubular zone or series of such zones. The materials ofconstruction employed should be inert to the materials present duringthe reaction and the fabrication of the equipment should be able towithstand the reaction temperatures and pressures. Means to introduceand/or adjust the quantity of starting materials or ingredientsintroduced batchwise or continuously into the reaction zone during thecourse of the reaction can be conveniently utilized in the processesespecially to maintain the desired molar ratio of the startingmaterials. For example, hydrogen and carbon monoxide may be fed inappropriate mole ratios, e.g., about 2:1, to maintain desired partialpressures. The reaction steps may be effected by the incrementaladdition of one of the starting materials to the other. Also, thereaction steps can be combined by the joint addition of the startingmaterials. When complete conversion is not desired or not obtainable,the starting materials can be separated from the product, for example bydistillation, and the starting materials then recycled back into thereaction zone.

The hydrocarbonylation processes may be conducted in either glass lined,stainless steel or similar type reaction equipment. The reaction zonemay be fitted with one or more internal and/or external heatexchanger(s) in order to control undue temperature fluctuations, or toprevent any possible "runaway" reaction temperatures.

The hydrocarbonylation processes of this invention may be conducted inone or more steps or stages. The exact number of reaction steps orstages will be governed by the best compromise between achieving highcatalyst selectivity, activity, lifetime and ease of operability, aswell as the intrinsic reactivity of the starting materials in questionand the stability of the starting materials and the desired reactionproduct to the reaction conditions.

The substituted and unsubstituted saturated alcohols produced by theprocesses of this invention can undergo further reaction(s) to afforddesired derivatives thereof. Such permissible derivatization reactionscan be carried out in accordance with conventional procedures known inthe art. Illustrative derivatization reactions include, for example,halogenation, amination, alkylation, dehydration, acylation,condensation, oxidation, silylation and the like, including permissiblecombinations thereof This invention is not intended to be limited in anymanner by the permissible derivatization reactions or permissiblederivatives of substituted and unsubstituted saturated alcohols.

For purposes of this invention, the term "hydrocarbon" is contemplatedto include all permissible compounds having at least one hydrogen andone carbon atom. Such permissible compounds may also have one or moreheteroatoms. In a broad aspect, the permissible hydrocarbons includeacyclic (with or without heteroatoms) and cyclic, branched andunbranched, carbocyclic and heterocyclic, aromatic and nonaromaticorganic compounds which can be substituted or unsubstituted.

As used herein, the term "substituted" is contemplated to include allpermissible substituents of organic compounds unless otherwiseindicated. In a broad aspect, the permissible substituents includeacyclic and cyclic, branched and unbranched, carbocyclic andheterocyclic, aromatic and nonaromatic substituents of organiccompounds. Illustrative substituents include, for example, alkyl,alkyloxy, aryl, aryloxy, hydroxy, hydroxyalkyl, amino, aminoalkyl,halogen and the like in which the number of carbons can range from 1 toabout 20 or more, preferably from 1 to about 12. The permissiblesubstituents can be one or more and the same or different forappropriate organic compounds. This invention is not intended to belimited in any manner by the permissible substituents of organiccompounds.

For purposes of this invention, the chemical elements are identified inaccordance with the Periodic Table of the Elements reproduced in "BasicInorganic Chemistry" by F. Albert Cotton, Geoffrey Wilkinson and Paul L.Gaus, published by John Wiley and Sons, Inc., 3rd Edition, 1995.

Certain of the following examples are provided to further illustratethis invention.

EXAMPLES 1-10

A 100 milliliter overhead stirred high pressure reactor was charged with0.25 mmol of dicarbonylacetylacetonato rhodium (I), about 0.95 mmol ofphosphine indicated in Table A below, 3 milliliters of 1,3-butadiene,about 22 grams or 26 milliliters of solvent/promoter indicated in TableA, and 1 milliliter of digylme as internal standard. The reactor waspressurized with 5-10 psi of 1/1 hydrogen/carbon monoxide, and heated toabout 80° C. At 80° C., the reactor was pressurized to 800 psi with 3/1hydrogen/carbon monoxide and stirred for 90 minutes. The reactor gaseswere vented and the reaction mixture drained and analyzed by gaschromatography. The results are set out in Table A.

                  TABLE A                                                         ______________________________________                                                                    Buta.       1-                                      Ex.   Conv. Rate Pentanol                                                     No. Ligand Solvent/Promoter % m/L/h %                                       ______________________________________                                        1    P(Octyl).sub.3                                                                          Di(ethylene glycol)                                                                        62    >0.3  78                                        ethyl ether                                                                 2 P(Octyl).sub.3 Methanol 93 1.3 51                                           3 P(CH.sub.2 Ph).sub.3 Pyrrole 87 >1.0 38                                     4 P(Octyl).sub.3 Acetamide 85 0.8 27                                          5 P(Octyl).sub.3 N-Methylacetamide 73 0.5 20                                  6 P(Octyl).sub.3 Diphenylamine 79 0.6 20                                      7 P(Octyl).sub.3 Diethyl-p-(N,N-di- 66 >0.3 24                                  Me-phenyl)                                                                    phosphine                                                                   8 P(Octyl).sub.3 EtOH/N,N,N,N- 86 1.4 29                                        Tetra-Me-                                                                     propanediamine                                                              9 P(Octyl).sub.3 THF/Phenol 84 0.8 26                                         10  P(Octyl).sub.3 THF/Phenol 73 0.4 65                                     ______________________________________                                    

Rates are reported at 20 minutes, and conversion and selectivities arereported at 90 minutes. Example 2 was conducted at a hydrogen partialpressure of 200 psi, a carbon monoxide partial pressure of 70 psi, and atemperature of 90° C. Example 3 was conducted at a hydrogen partialpressure of 200 psi and a carbon monoxide partial pressure of 600 psi.

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

We claim:
 1. A process for producing one or more substituted or unsubstituted saturated alcohols which comprises reacting one or more substituted or unsubstituted alkadienes with carbon monoxide and hydrogen in the presence of a homogeneous rhodium-ligand complex catalyst and a promoter and optionally free ligand to produce said one or more substituted or unsubstituted saturated alcohols, wherein said promoter comprises an organic or inorganic compound with an ionizable hydrogen of pKa of from about 1 to about
 35. 2. A process for producing one or more substituted or unsubstituted saturated alcohols which comprises reacting one or more substituted or unsubstituted alkadienes with carbon monoxide and hydrogen in the presence of a homogeneous rhodium-organophosphorus ligand complex catalyst and a promoter and optionally free organophosphorus ligand to produce said one or more substituted or unsubstituted saturated alcohols, wherein said promoter comprises an organic or inorganic compound with an ionizable hydrogen of pKa of from about 1 to about
 35. 3. A process for producing one or more substituted or unsubstituted 1-pentanols which comprises reacting one or more substituted or unsubstituted butadienes with carbon monoxide and hydrogen in the presence of a homogeneous rhodium-organophosphorus ligand complex catalyst and a promoter and optionally free organophosphorus ligand to produce said one or more substituted or unsubstituted 1-pentanols, wherein said promoter comprises an organic or inorganic compound with an ionizable hydrogen of pKa of from about 1 to about
 35. 4. The process of claim 3 wherein the substituted or unsubstituted butadienes comprises butadiene and the substituted or unsubstituted 1-pentanols comprise 1-pentanol.
 5. The process of claim 3 which is conducted at a hydrogen partial pressure and carbon monoxide partial pressure sufficient to prevent or minimize formation of substituted or unsubstituted lactols, diols and/or hydroxyaldehydes.
 6. The process of claim 1 wherein said rhodium-ligand complex catalyst comprises rhodium complexed with an organophosphine ligand selected from a mono-, di-, tri- and poly-(organophosphine) ligand.
 7. The process of claim 1 wherein said rhodium-ligand complex catalyst comprises rhodium complexed with an organophosphine ligand selected from a triorganophosphine ligand represented by the formula: ##STR3## wherein each R¹ is the same or different and is a substituted or unsubstituted monovalent hydrocarbon radical.
 8. The process of claim 7 wherein each R¹ is the same or different and is selected from primary alkyl, secondary alkyl, tertiary alkyl and aryl.
 9. The process of claim 3 wherein the organophosphorus ligand has a basicity greater than or equal to the basicity of triphenylphosphine (pKb=2.74) and a steric bulk lower than or equal to a Tolman cone angle of 210°.
 10. The process of claim 3 wherein the promoter is incorporated into the ligand structure either as the rhodium-ligand complex catalyst or as free ligand.
 11. The process of claim 3 wherein the promoter has a pKa of about 1-35 and comprises a protic solvent, organic and inorganic acid, alcohol, water, phenol, thiol, selenol, nitroalkane, ketone, nitrile, amine, amide, or a mono-, di- or trialkylammonium salt or mixtures thereof.
 12. The process of claim 3 which is conducted at a temperature from about 50° C. to 150° C. and at a total pressure from about 20 psig to about 3000 psig.
 13. A process for producing a batchwise or continuously generated reaction mixture comprising:(1) one or more substituted or unsubstituted 1-pentanols; (2) optionally one or more substituted or unsubstituted cis-2-pentenols, trans-2-pentenols, cis-3-pentenols, trans-3-pentenols and/or 4-pentenols; (3) optionally one or more substituted or unsubstituted cis-2-pentenals, trans-2-pentenals, cis-3-pentenals, trans-3-pentenals and/or 4-pentenals; (4) optionally one or more substituted or unsubstituted valeraldehydes; (5) optionally one or more substituted or unsubstituted lactols, diols and/or hydroxyaldehydes, e.g., 2-methylvalerolactol, 2-ethylbutyrolactol, 2-methyl-1,5-pentanediol, 2-ethyl-1,4-butanediol, 1,6-hexanediol and 6-hydroxyhexanal; and (6) one or more substituted or unsubstituted butadienes, e.g., butadiene;wherein the weight ratio of the sum of component (1) to the sum of components (2), (3), (4) and (5) is greater than about 0.1, preferably greater than about 0.25, more preferably greater than about 1.0; and the weight ratio of component (6) to the sum of components (1), (2), (3), (4) and (5) is about 0 to about 100, preferably about 0.001 to about 50; which process comprises reacting one or more substituted or unsubstituted butadienes with carbon monoxide and hydrogen in the presence of a homogeneous rhodium-organophosphorus ligand complex catalyst and a promoter and optionally free organophosphorus ligand to produce said batchwise or continuously generated reaction mixture, wherein said promoter comprises an organic or inorganic compound with an ionizable hydrogen of pKa of from about 1 to about
 35. 14. A process for producing a reaction mixture comprising one or more substituted or unsubstituted saturated alcohols which process comprises reacting one or more substituted or unsubstituted alkadienes with carbon monoxide and hydrogen in the presence of a homogeneous rhodium-ligand complex catalyst and a promoter and optionally free ligand to produce said reaction mixture comprising one or more substituted or unsubstituted saturated alcohols, wherein said promoter comprises an organic or inorganic compound with an ionizable hydrofgen of pKa of from about 1 to about
 35. 15. A process for producing a reaction mixture comprising one or more substituted or unsubstituted 1-pentanols which process comprises reacting one or more substituted or unsubstituted butadienes with carbon monoxide and hydrogen in the presence of a homogeneous rhodium-organophosphorus ligand complex catalyst and a promoter and optionally free organophosphorus ligand to produce said reaction mixture comprising one or more substituted or unsubstituted 1-pentanols, wherein said promoter comprises an organic or inorganic compound with an ionizable hydrogen of pKa of from about 1 to about
 35. 16. A batchwise or continuously generated reaction mixture comprising:(1) one or more substituted or unsubstituted 1-pentanols; (2) optionally one or more substituted or unsubstituted cis-2-pentenols, trans-2-pentenols, cis-3-pentenols, trans-3-pentenols and/or 4-pentenols; (3) optionally one or more substituted or unsubstituted cis-2-pentenals, trans-2-pentenals, cis-3-pentenals, trans-3-pentenals and/or 4-pentenals; (4) optionally one or more substituted or unsubstituted valeraldehydes; (5) optionally one or more substituted or unsubstituted lactols, diols and/or hydroxyaldehydes, e.g., 2-methylvalerolactol, 2-ethylbutyrolactol, 2-methyl-1-1,5-pentanediol, 2-ethyl-1-1,4-butanediol, 1,6-hexanediol and 6-hydroxyhexanal; and (6) one or more substituted or unsubstituted butadienes, e.g., butadiene;wherein the weight ratio of the sum of component (1) to the sum of components (2), (3), (4) and (5) is greater than about 0.1, preferably greater than about 0.25, more preferably greater than about 1.0; and the weight ratio of component (6) to the sum of components (1), (2), (3), (4) and (5) is about 0 to about 100, preferably about 0.001 to about
 50. 17. A reaction mixture comprising one or more substituted or unsubstituted saturated alcohols in which said reaction mixture is prepared by a process which comprises reacting one or more substituted or unsubstituted alkadienes with carbon monoxide and hydrogen in the presence of a homogeneous rhodium-ligand complex catalyst and a promoter and optionally free ligand to produce said reaction mixture comprising one or more substituted or unsubstituted saturated alcohols, wherein said promoter comprises an organic or inorganic compound with an ionizable hydrogen of pKa of from about 1 to about
 35. 18. A reaction mixture comprising one or more substituted or unsubstituted 1-pentanols in which said reaction mixture is prepared by a process which comprises reacting one or more substituted or unsubstituted butadienes with carbon monoxide and hydrogen in the presence of a homogeneous rhodium-organophosphorus ligand complex catalyst and a promoter and optionally free organophosphorus ligand to produce said reaction mixture comprising one or more substituted or unsubstituted 1-pentanols, wherein said promoter comprises an organic or inorganic compound with an ionizable hydrogen of pKa of from about 1 to about
 35. 19. The reaction mixture of claim 18 in which the process further comprises derivatizing said one or more substituted or unsubstituted 1-pentanols.
 20. A derivative of the one or more substituted or unsubstituted 1-pentanols of claim
 19. 